The dye-sensitized TiO2 method is one of the most promising methods for the visible-light-induced detoxification of pollutants. The reaction mechanism for photocatalytic degradation of orange II (OII) and rhodamine B (RhB) with self-sensitized TiO2 under visible light irradiation (λ > 400 nm) has been evaluated. Radical scavenger studies were carried out to investigate the active species involved in the photodegradation of 5 mg/L of initial concentration of OII and RhB at room temperature. The trapping effects of different scavengers results proved that the oxidation of OII and RhB mainly occurred by the direct oxidization of h+ and ·O2- radicals, while the ·OH radicals played only a relatively minor role in the direct oxidization process.